EP3523828A1

EP3523828A1 - Improved contacts for a photovoltaic cell having two active faces

Info

Publication number: EP3523828A1
Application number: EP17780381.4A
Authority: EP
Inventors: Pierre-Philippe Grand; Daniel Lincot
Original assignee: Electricite de France SA; Centre National de la Recherche Scientifique CNRS; Paris Sciences et Lettres Quartier Latin
Current assignee: Electricite de France SA; Centre National de la Recherche Scientifique CNRS; Paris Sciences et Lettres Quartier Latin
Priority date: 2016-10-05
Filing date: 2017-10-04
Publication date: 2019-08-14
Anticipated expiration: 2037-10-04
Also published as: WO2018065478A1; CN110168740A; US10998457B2; US20190296162A1; EP3523828B1; FR3057106B1; FR3057106A1; CN110168740B

Abstract

The invention relates in particular to the production of a bifacial photovoltaic cell, with two opposite active faces, comprising a step of depositing, on each active face, at least one electrical contact. The deposition step comprises, in particular, a common deposition operation on each of the active faces, implemented by electrolysis in a common electrolysis tank comprising: - a first compartment (C1) for depositing a metal layer on a first active face of the cell, in order to produce a contact comprising said metal layer on the first active face, and - a second compartment (C2) for depositing, by oxidation, a conductive metal oxide layer on the second active face of the cell, in order to produce a contact comprising said metal oxide layer on the second active face.

Description

Advanced Contacts of a Photovoltaic Cell with Two Active Faces

The invention lies in the field of the manufacture of photo voltaic cells, and is more particularly related to the deposition of contacts on such cells.

In the case, for example, where such cells are based on silicon, the cells currently dominating the photovoltaic market are mono-faceted (only one active face receiving the light rays), the rear face being entirely metallized. Nevertheless, for the purpose of increasing photovoltaic conversion efficiencies, the development of so-called "bifacial" cells is currently experiencing a great expansion. Indeed, in these structures with two opposite active faces, the efficiency of the panel is the sum of the yield obtained on the front face (direct radiation) and that obtained on the back side (which receives only the reflected radiation - about 20 % of the light incident on grass, for example). The order of magnitude of conversion gain with respect to a mono-facial cell is therefore about 3 to 4% absolute, depending on the rate of reflection of the incident surface (turf, snow, sand, etc.). Nevertheless, the development of bifacial cells is slowed down because of the high cost of their production as well as the performance limitations related in particular to the use of screen printing based on silver paste for the metallization of metal contacts.

An alternative to screen-printing metallization is the use of electrochemical plating, which is beginning to be industrialized for mono-facial cells. The general interest of the electrochemical veneer compared to the screen printing is:

- from a performance point of view:

- reduce the shading rate of the cell by reducing the size of the metallized pattern (width of the collecting fingers can be reduced by more than 50%), - allow the contact of highly resistive transmitters (> 120Ω),

improve the electrical conductivity and decrease the contact resistance with the transmitter,

- from an economic point of view :

suppress (or decrease very strongly) the quantity of silver and replace it with copper (with a factor gain of 100 on the cost of the metal), replace screen printing with an electrochemical method (with a better rate of use of raw material).

Electrochemical plating is not possible by conventional electrolysis (due to the excessive resistivity of silicon), the most commonly used approach is a so-called "mixed" approach to thickening screen-printed contacts.

Certain properties of the silicon substrate can also be stimulated and two common electrochemical techniques for direct plating on a silicon substrate are:

light induced deposition (LIP), and

- The deposit in the direction of polarization of the diode (called "Forward Bias Plating" or FBP).

Light induced deposition (LIP) is used for the metallization of the n ^{+ side} . In this case, by illuminating the semiconductor, the pn junction generates electron-hole pairs. By applying a potential between an anode to the rear face (p) of the previously metallized photovoltaic cell, the electrons generated are used on the n ^{+ side} to reduce the metal salts present in the deposition bath.

However, the "competition" on the p ^{+ side} between the formation of holes (linked to photo-generation of the current) and the arrival of electrons to feed the reduction reaction on the n ^{+ side} is incompatible with the formation of a compound by electrolysis on a bifacial cell. Thus, in a LIP type technique, the rear face of the cell is often out of electrolysis bath to prevent problems of corrosion or over-deposit. The polarization diode deposition technique (FBP) is used for the metallization of the p ^{+ side} . In this case, by connecting an anode to the rear face of the solar cell (n ⁺ ), a potential or cathodic current is applied to the back face previously metallized. This potential is used to generate electrons that pass through the diode and are available on the p ^{+ side} . However, again this technique is not usable for a bifacial cell because if both sides are exposed to the electrolysis bath, the application of the potential (or current) leads to the formation of a compound by reduction on the face n ⁺ . The formation of this conductive compound "blocks" then the flow of electrons through the diode and only a deposit on the n ^{+ side} is obtained. Of course, it is possible to provide a combination of the two techniques (LIP and FBP) to achieve the metallization of bifacial cells, but this combination requires a heavy and complex implementation (necessarily sequential metallization, management of the electrical contact and transmission lines). fields between the two faces, need a precise alignment between the openings of the two faces).

The only technique of metallization (electro-chemical) for simultaneously depositing a metal on both sides of the silicon (one of the p ⁺ type and the other type n) is a so-called electroless electroless method. It nevertheless has disadvantages: complexity of implementation, need for activation of the surface prior to deposition (often using a bath containing palladium, expensive metal), long deposit time (~ 0, ^ m / min), short bath life and delicate bath management, at a high deposition temperature (above 80 ° C). Moreover, the deposition rate depends on the type of surface to be covered (with a different selectivity on the faces of the cell).

It is then desired simultaneous electrochemical deposition of the contacts of the front and rear face of the bifacial cell which is more suitable, in terms of ease of implementation, deposition rate, etc.

The present invention improves this situation.

To this end, it proposes a method of manufacturing a bifacial photovoltaic cell, with two opposite active faces, comprising a step of depositing, on each active face, at least one electrical contact. The deposition step comprises in particular a common deposition operation on each of the active faces, implemented by electrolysis in a common electrolytic cell comprising:

a first compartment for the deposition of a metal layer on a first active face of the cell, for the manufacture of a contact comprising said metal layer on the first active face, and

a second compartment for depositing, by oxidation, a conductive metal oxide layer on the second active face of the cell, for the manufacture of a contact comprising said metal oxide layer on the second active face. For example, the metal of the metal oxide layer may be at least one of Mn, Ni, Mo, Cd, Sn, In, Zn, Pb, Ag, Cu, In, Ga, Co, W, Ta, Ga and TI.

More particularly, during the joint deposit operation:

electrons are generated in the first compartment, facing the first active face, to promote the deposition of the metal layer, and

- Holes are generated in the second compartment, facing the second active face, to promote the oxidation deposition of the metal oxide layer. In one embodiment, the first and second compartments are separated by an ion exchange membrane that includes the electrolysis cell.

Preferably, the deposit:

the metal layer on the first active face, and

the metal oxide layer on the second active face,

is assisted by illumination of at least one of the first and second active faces.

Indeed, the lighting promotes the generation of electron / hole pairs and therefore the simultaneous deposition of the metal layer and the metal oxide layer. This lighting can be performed on at least one of the two faces.

Optionally, the deposition operation is assisted by applying a potential difference capable of generating at least negative charges on the first active face.

Alternatively or in addition, the deposition operation may be assisted by applying a potential difference that is capable of generating positive charges on the second active face.

In one embodiment, the photovoltaic cell is bifacial homo-junction, n + type on the first active face and p + on the second active face.

The bulk material (or "bulk", also called substrate SUB hereafter) may be for example silicon, n or p type. The surfaces of the material remain however:

- of type p ⁺ on one side,

and of type n ⁺ on the opposite opposite side. As indicated by way of example above, the photovoltaic cell may be based on silicon.

In one possible embodiment, the metal layer on the first active face may be nickel-based, and the electrical contact deposition step on this first active face may then be continued by the deposition on the metal layer of a layer comprising at least copper, by electrolysis. This solution is very advantageous economically because it comes to replace the deposit of a silver paste, expensive, usually made by screen printing.

The step of depositing electrical contact on the second active face can also be continued by the deposition on the metal oxide layer of a layer comprising at least copper, by electrolysis (since the oxide is conductive). As will be seen with reference to Figure 1 commented in detail later, the contact deposition step is preceded by a step of etching at least one electrically insulating layer (Si0 ₂ , SiN _x ), deposited on each side active. This etching exposes each active face in a region in which the above-mentioned simultaneous deposition electrolysis operation can then be applied.

The present invention also relates to a bifacial photovoltaic cell with two opposite active faces, the cell having on each active face at least one electrical contact. In particular, the contact of a first active face comprises a metal layer deposited on the first active face, while the contact of the second active face comprises a conductive metal oxide layer deposited on the second active face.

The difference of the contact material between the two faces, with in particular:

- one of metal, and

- the other in conductive metal oxide,

mark a trace of the process on the cell obtained by the implementation of this method of the invention and thus, such a cell can be obtained by the implementation of the method above. As indicated above, the cell may be of the homo-junction type, of type n on the first active face and p ⁺ on the second active face.

Other advantages and characteristics of the invention will appear on reading the following detailed description of embodiments of the invention, and on examining the appended drawings in which:

FIG. 1 shows an embodiment for the manufacture by electrolysis of a cell within the meaning of the invention,

FIG. 2 shows an example of a cell within the meaning of the invention,

FIGS. 3 to 5 show alternative embodiments to that of FIG. 1, for the electrolytic manufacture of a cell within the meaning of the invention,

In the embodiment described hereinafter, it is proposed to use the semiconducting property of the PN junction of the bifacial photovoltaic cell: the illumination of at least one of the two faces leads to the photo- generation of electron / hole pairs. Electrons are generated on the n ^{+ side} and "holes" on the p ^{+ side} . It is therefore possible to carry out an electrochemical reduction reaction on the n ^{+ side} (and thus to deposit a metal), and in parallel, to promote an electrochemical oxidation reaction on the opposite face p ⁺ (thus to deposit a metal oxide typically).

Thus, without the necessary connection to an external circuit, if the photovoltaic material of the cell (for example silicon) is in contact with two suitable electrolytes (one per face), it is therefore possible to perform a simultaneous deposition:

on the n ⁺ doped side: the electro-deposition of a metal (for example nickel),

on the p ⁺ doped side: the electro-deposition of a metal oxide (for example MnO ₂ , O, MoO ₃ , CdO, SnO ₂ , etc.).

Thus, with reference to FIG. 1, the substrate SUB (for example of silicon), with photovoltaic properties, and comprising opposite first and second active faces (doped n + and p + respectively) is immersed in an electrolysis vessel BA. An ion exchange ME membrane (anionic or cationic) is further provided in the extension of the substrate SUB to close two respective compartments C1 and C2 in the tank. The ECL illumination of at least one of the faces favors the photo-generation of electrons ne- on the first face (in the compartment C1) and holes TR on the second face (in the compartment C2). The electrons in the compartment C1 allow the deposition of the metal (for example nickel Ni) on the free surface of the substrate (between the two silicon nitride masks SiN _x ). Parallel and simultaneously in particular in the compartment C2, it creates "holes" (positive charges) promoting the deposition of metal oxide, and in particular the deposition of a conductive oxide (e.g., Mn0 ₂ or other as shown in the examples below). In particular, the electrochemically deposited metal oxide on the p ^{+ side} preferably has the following properties. This is a:

Nickel equivalent electrical conductor (14.10 ⁶ S / m) forming an ohmic contact with silicon

and barrier to the diffusion of copper in silicon

- without degrading under heat treatment (range 350-550 ° C) for the subsequent steps of manufacture of the cell,

while minimizing the level of impurities (eg carbon) in the resulting layer. In addition, if this oxide is transparent and conductive (such as titanium oxide or ITO), it can allow electrical collection and allowing the incident light to pass (reduced shading rate).

Preferably, on this oxide, one can advantageously deposit copper by electrolysis to increase the conductivity of the electrical contacts. Then, a thin layer of silver can be deposited on the copper to protect it from oxidation and improve its weldability in order to manufacture assembled photovoltaic modules. Finally, a heat treatment can be performed to allow the n ^{+ side} to form NiSi, which has a role of ohmic contact on silicon and prevention of diffusion of copper. Thus, the solar cell may have a stack of the type illustrated in FIG. 2 (in an exemplary embodiment relating to a bifacial cell here of the N-PERT type, for "Passivated Emitter, Rear Totally Diffused"), in which:

the reference MO _x generally denotes a metal oxide with M preferentially but not limitatively at least one of the elements: Mn, Cr, Fe, Co,

Ni, Cu, Zn, Cd, W, Mo, In, Ga, Ta, V. The noble metals (Pd, Pt, Au, Ag) can also be considered with, however, a higher manufacturing cost;

the reference SiN _x denotes silicon nitride (s) (and SiO ₂ of the silica). Using an electrochemical technique for the formation of electrical contacts has many advantages (compared to the usual technique which is screen printing):

- reduction of the manufacturing cost (in particular by reducing the amount of money to be deposited), and

- increased performance (contact of highly resistive transmitters, improvement of the shading rate, better conductivity).

In addition, the use of the illumination of a photovoltaic substrate for wet deposition on both sides, simultaneously and without contact with an external circuit, metal-based layers (including an oxide) also has advantages:

it makes it possible to use the photocurrent generated by the diode for electro-depositing the metal and the metal oxide.

the connection to an external circuit is not necessary because the oxy-reduction torque on each of the two faces is directly at the photovoltaic substrate / electrolyte interface.

More specifically, with reference again to FIG. 1, the phenomena used are:

the photo-generation of electrons on the n ^{+ side} in contact with a reducible compound in the compartment C1, with a reaction of the type: Oxi + ne ^" Redi

- -génération the photo of "holes" on the p + side in contact with an oxidizable compound in the compartment C2, with a reaction of the type: Red ₂ Ox ₂ + ne ^" To avoid acidification or alkalinization of one of the compartments, an ion exchange membrane (Nafion type, anionic or cationic) can separate the two compartments and maintain the ionic balance. The illumination device may comprise a row of diodes or halogen lamps having a maximum of electromagnetic irradiation in the red near-infrared visible region. The irradiation may preferably include the domain of ultraviolet optical wavelengths to activate and / or catalyze the electrolyte / silicon interface in order to promote the nucleation of the first deposition seeds on the surface of the silicon.

Depending on the electrochemical reactions involved, the illumination may advantageously be applied on both sides, making it possible to adjust the electrochemical potentials on both sides if necessary. The photo-generated current (of an order of magnitude of a few tens of mA.cm ^" ), makes it possible to reach deposit rates at least 10 times higher than those obtained by an autocatalytic type process (" electroless "process, the most effective known at present) The activation stage of the electroless process (starting of the nucleation of the Nickel Ni contact, for example with Palladium particles) is not necessary. simpler and more stable than electroless baths and allow for purer deposits (less carbon-like impurities in the resulting film) .The overall process is therefore faster and less expensive than the electroless process, with equivalent photo voltaic performance. More generally, the implementation in the sense of the present invention has many advantages over known techniques, such as the screen printing technique, Electr oless and torque LIP / FBP Already, the treatment of the invention is simultaneous, fast and without electrical contact of the two faces of the bifacial solar cells for the formation of electrical collection grids by preferentially using the illumination of one of the two faces . More particularly, with respect to the electroless method, the technique of the invention makes it possible:

- incorporation of less impurities (such as carbon, or phosphorus) into the deposits;

a saving in manufacturing time by the simultaneous treatment of both faces and a high deposition rate,

- Bath management easier in terms of bath life, recharge, deposition temperature. In relation to the screen printing method, the invention notably provides an improvement in the performance of photovoltaic devices with:

a decrease in the shading rate of the cell by reducing the size of the metallized pattern (width of the collecting fingers being able to be reduced by more than 50%),

an improvement in the contact of highly resistive transmitters (> 120Ω),

an improvement of the electrical conductivity and a reduction of the contact resistance with the emitter.

as well as a manufacturing economy by:

- suppression (or strong decrease) of Silver by replacing it with Copper,

replacement of screen printing by an electrochemical method (less expensive).

Some specific embodiments are presented hereinafter.

In a first exemplary embodiment presented below, simultaneous deposition of MnO ₂ on the p ⁺ face and Nickel on the n ^{+ side is carried out} .

In a tank with two compartments separated by a cation exchange membrane Nafion, using a seal system ensuring the sealing of both sides, a nickel metallization bath is placed in the compartment n ⁺ (Cl) and a metallization bath of MnO ₂ in the compartment p ⁺ (C2). The (Silicon) substrate is illuminated with a row of white LED lamps on one side. For Ni deposition, in a Watts bath, a temperature of 60 ° C is applied for 2 minutes. Nickel is deposited according to the following general reaction:

Ni ²⁺ + 2e ^" -> Ni

2H ⁺ + 2e ^" -> H ₂

Meanwhile, for the deposition of Mn0 _2, in a bath including 0.01 M Mn (C ₂ H ₃ 0 ₂₎ ₂ (called "Mn acetate"), 0.02 M NH ₄ (C ₂ H ₃ 0 ₂ ) (called "ammonium acetate") and 10% C ₂ ¾OS (dimethyl sulfoxide (DMSO)), a temperature of 60 ° C is applied for two minutes. The manganese oxide is then deposited anodically according to the following general reaction:

Mn ²⁺ + 2H ₂ 0 → Mn0 ₂ + 4H ⁺ + 2e

The ion exchange membrane advantageously allows the protons (H ⁺ ) to be balanced between the two compartments.

On both sides simultaneously, copper can be deposited by direct electrolysis to increase the conductivity of the electrical contacts. Then, a thin layer of silver can be deposited on the copper to protect it from oxidation and improve its weldability in order to manufacture photo voltaic modules. Finally, a heat treatment (range 350 - 550 ° C) can be performed to allow the formation of NiSi alloy on the n ^{+ side} , which has a role of ohmic contact on the silicon and prevention of diffusion of copper.

In a second embodiment, cadmium oxide CdO is deposited on the p ^{+ side} and nickel is deposited on the n ^{+ side} .

The deposit of CdO can be carried out at ambient temperature in 0.05M of cadmium acetate [Cd (C ₂ H ₃ O ₂ ) ₂ ] and 0.1M of Na ₂ SO ₄ .

The same procedure as that described in the first embodiment can then be applied (nickeling on the n ^{+ side} , simultaneous coppering on both sides, silvering and heat treatment). In a third embodiment, SnO ₂ tin oxide is deposited on the p face and nickel on the n ^{+ side} , providing in the DMSO, 0.1 M SnCl ₂ and 0.5 M NaNO ₃ . In a fourth embodiment, manganese oxide MnO ₂ is deposited on the p ⁺ face and nickel on the n ⁺ face with a single deposition bath because in this case, the two faces of the substrate are exposed to the same surface. electrolyte which contains at least one nickel salt (for example a sulphate) and a manganese salt Mn (for example an acetate). By application of standard electrochemical reaction potentials, the nickel salt reduction reaction takes place at the cathode and the formation of the manganese oxide at the anode. In the case of a single bath, the ion exchange membrane is no longer necessary (ionic equilibrium established by the exchange of protons between the reactions at the anode and the cathode). Of course, the present invention is not limited to the embodiments presented above as examples; it extends to other variants.

The principle of photo-generation of the current for example admits variant embodiments. Typically, it can be further assisted by applying a potential between the p ⁺ and n ⁺ terminals of the substrate (preferential range of 0 to 2V). The direction of polarization is shown in Figure 3.

Alternatively, with respect to this embodiment, it is possible to provide a specific electrode for the reaction and different from the substrate. The principle of photo-generation of the current remains the same but it is assisted by application of a potential between the n ⁺ terminal of the substrate and an anode (preferred range of 0 to 2V). The polarization direction is shown in Figure 4. The anode may be is soluble (e.g. nickel, preferably) or insoluble (e.g. Ti0 ₂ oxide / IR0 _2). Alternatively, the direction of polarization may be as described in FIG. 5. In this case, the cathode is preferably insoluble (for example in oxide Ti0 ₂ / Ir0 ₂ ). Furthermore, it has been described above the use of illumination to promote reactions in the two compartments of the electrolysis cell. This embodiment is advantageous in the case of a silicon substrate in particular. Nevertheless, it is not necessarily necessary for example for a substrate other than silicon. Typically, in some cases of substrate, the electrical stimulation presented in one of FIGS. 3 to 5 could suffice, for example.

Claims

1. A method for manufacturing a bifacial photovoltaic cell, with two opposite active faces, comprising a deposition step, on each active face, of at least one electrical contact, characterized in that the deposition step comprises a common operation deposition on each of the active faces, implemented by electrolysis in a common electrolytic cell comprising:

a second compartment for depositing, by oxidation, a conductive metal oxide layer on the second active face of the cell, for the manufacture of a contact comprising said metal oxide layer on the second active face.

2. Method according to claim 1, characterized in that the metal of the metal oxide layer is at least one of Mn, Ni, Mo, Cd, Sn, In, Zn, Pb, Ag, Cu, W, Ta , Ga, Fe, Co, Cr and Ti.

3. Method according to one of the preceding claims, characterized in that, during the common deposition operation:

- Holes are generated in the second compartment, facing the second active face, to promote the oxidation deposition of the metal oxide layer.

4. Method according to one of the preceding claims, characterized in that the first and second compartments are separated by an ion exchange membrane that includes the electrolytic cell.

5. Method according to one of the preceding claims, characterized in that the deposit:

the metal layer on the first active face, and

the metal oxide layer on the second active face,

6. Method according to one of the preceding claims, characterized in that the deposition operation is assisted by applying a potential difference to generate negative charges on the first active face.

7. Method according to one of the preceding claims, characterized in that the deposition operation is assisted by applying a potential difference to generate positive charges on the second active face.

8. Method according to one of the preceding claims, characterized in that the photovoltaic cell is bifacial homo-junction, n ⁺ type on the first active face and p ⁺ on the second active face.

9. Method according to one of the preceding claims, characterized in that the photovoltaic cell is based on silicon.

10. Method according to one of the preceding claims, characterized in that the metal layer on the first active face is nickel-based, and in that the step of depositing electrical contact on the first active face continues with the depositing on the metal layer a layer comprising at least copper, by electrolysis.

11. Method according to one of the preceding claims, characterized in that the step of depositing electrical contact on the second active face continues with the deposition on the metal oxide layer of a layer comprising at least copper, by electrolysis.

12. Method according to one of the preceding claims, characterized in that the contact deposition step is preceded by a step of etching at least one electrically insulating layer (Si0 ₂ , SiN _x ), deposited on each active face. said etching exposing each active face in a region in which the electrolysis deposition operation is applied.

13. Bifacial photovoltaic cell, with two opposite active faces, the cell having on each active face at least one electrical contact, characterized in that the contact of a first active face comprises a metal layer deposited on the first face active, and in that the contact of the second active face comprises a conductive metal oxide layer deposited on the second active face.

14. Cell according to claim 13, characterized in that it comprises a homojunction of n ⁺ type on the first active face and p ⁺ on the second active face.

15. Cell according to one of claims 13 and 14, characterized in that it is obtained by the implementation of the method according to one of claims 1 to 12.